Thermal decomposition of polylactic acid （PLA） was studied in the presence of pine wood sawdust （PS）, walnut shell （WS）, corncob （CC） in order to understand the pyrolytic behavior of these components occurring...Thermal decomposition of polylactic acid （PLA） was studied in the presence of pine wood sawdust （PS）, walnut shell （WS）, corncob （CC） in order to understand the pyrolytic behavior of these components occurring in waste. A thermogravimetric analyzer （TGA） was applied for monitoring the mass loss profiles under heating rate of 10℃·min^-1. Results obtained from this comprehensive investigation indicated that PLA was decomposed in the temperature range 300 -372℃, whereas the thermal degradation temperature of biomass is 183-462℃. The difference of mass loss （AW） between experimental and theoretical ones, calculated as algebraic sums of those from each separated component, is about 17%-46% at 300-400℃. These experimental results indicated a significant synergistic effect during PLA and biomass copyrolysis. Moreover, a kinetic analysis was performed to fit thermogravimetric data, the global processes being considered as one to two consecutive reactions. A reasonable fit to the experimental data was obtained for all materials and their blends.展开更多
This study investigated catalytic decomposition and mass transfer of aqueous ozone promoted by Fe-MnCu/γ-Al_(2)O_(3)(Cat)in a rotating packed bed(RPB)for the first time.The results showed that the value of the overal...This study investigated catalytic decomposition and mass transfer of aqueous ozone promoted by Fe-MnCu/γ-Al_(2)O_(3)(Cat)in a rotating packed bed(RPB)for the first time.The results showed that the value of the overall decomposition rate constant of ozone(K_(c))and overall volumetric mass transfer coefficient(K_(L)a)are 4.28×10^(-3) s^(-1) and 11.60×10^(-3) s^(-1) respectively at an initial pH of 6,βof 40,Co3(g)of 60 mg·L^(-1)and Q_(L) of 85 L·h^(-1) in deionized water,respectively.Meanwhile,the K_(c) and K_(L)a values of Fenhe water are0.88×10^(-3) s^(-1) and 2.51×10^(-3) s^(-1) lower than deionized water,respectively.In addition,the K_(c) and K_(L)a values in deionized water for the Cat/O_(3)-RPB system are 44.86%and 47.41%higher than that for the Cat/O_(3)-BR(bubbling reactor)system,respectively,indicating that the high gravity technology can facilitate the decomposition and mass transfer of ozone in heterogeneous catalytic ozonation and provide some insights into the industrial wastewater.展开更多
CO and formaldehyde(HCHO)oxidation reactions were investigated over mesoporous Ag/Co3O4 catalysts prepared by one-pot(OP)and impregnation(IM)methods.It was found that the one-pot method was superior to the impregnatio...CO and formaldehyde(HCHO)oxidation reactions were investigated over mesoporous Ag/Co3O4 catalysts prepared by one-pot(OP)and impregnation(IM)methods.It was found that the one-pot method was superior to the impregnation method for synthesizing Ag/Co3O4 catalysts with high activity for both reactions.It was also found that the catalytic behavior of mesoporous Co3O4 and Ag/Co3O4 catalysts for the both reactions was different.And the addition of silver on mesoporous Co3O4 did not always enhance the catalytic activity of final catalyst for CO oxidation at room temperature(20 C),but could significantly improve the catalytic activity of final catalyst for HCHO oxidation at low temperature(90 C).The high surface area,uniform pore structure and the pretty good dispersion degree of the silver particle should be responsible for the excellent low-temperature CO oxidation activity.However,for HCHO oxidation,the addition of silver played an important role in the activity enhancement.And the silver particle size and the reducibility of Co3O4 should be indispensable for the high activity of HCHO oxidation at low temperature.展开更多
Understanding the impact of biological activities on the soil phosphorus(P)distribution under long-term fertilizer application can facilitate better soil P fertility management.Therefore,the primary objectives of this...Understanding the impact of biological activities on the soil phosphorus(P)distribution under long-term fertilizer application can facilitate better soil P fertility management.Therefore,the primary objectives of this study were to investigate the effect of long-term(since 1981)fertilizer application on the soil P fractions and microbial community and to evaluate correlations between the microbial community structure and P distribution.The following treatments were implemented in a long-term field trial:no fertilization(CK),inorganic N and K(NK),inorganic P and K(PK),inorganic N,P and K(NPK)and manure+NPK(MNPK)fertilization.The study showed that the soil pH,soil organic carbon and total and available N and P concentrations were considerably higher in the MNPK treatment than in the CK treatment.The soil microbial biomass C,N and P concentrations were also significantly higher in the MNPK treatment than in the CK treatment.Among fertilization treatments,theβ-1,4-glucosidase,α-1,4-glucosidase,urease,acid phosphatase and phosphodiesterase activities were the highest in the MNPK treatment.Compared to inorganic fertilization,the MNPK treatment increased the labile soil P fractions and decreased the residual soil P concentration.Continuous fertilization significantly affected the soil microbial composition.The total phospholipid fatty acid(PLFA)concentrations in the NK,PK,NPK and MNPK treatments were 23.3,43.1,48.7 and 87.7%higher,respectively,than in the CK treatment.A significant correlation was observed between the microbial community and soil P fractions.Moreover,the aggregated boosted tree(ABT)model showed that among the various soil biochemical properties,the total PLFA concentration was the factor that most influenced the active P pool,accounting for 35.4%of the relative influence of all soil biochemical properties examined.These findings reveal that combined manure and inorganic fertilizer application is a better approach than applying inorganic fertilizer alone for sustaining long-term P fertility by mediating soil biological activity.展开更多
Fresh TiO2 was found to possess a strong germicidal activity even without UV irradiation. Live Yeast （Saccharomyces cerevisiae） cells in contact with fresh TiO2 were found deformed and dead after 15min contact. The ...Fresh TiO2 was found to possess a strong germicidal activity even without UV irradiation. Live Yeast （Saccharomyces cerevisiae） cells in contact with fresh TiO2 were found deformed and dead after 15min contact. The cause of germicidal activity was discussed from the observed cell deformation, lysis and increased absorption at 1680 cm^-1 in FT-IR spectra of the affected cells, which proved the oxidizing effect of fresh TiO2 to cells. The deformation caused by the stretching of cell wail and pressure built-up inside the cell, led to cell burst and release of intracellular materials. The degree of cell deformation was found positively related with the wetting property of TiO2. Cells are negatively charged, for Gram-negative cell （thinner ceil wail）, a higher germicidal effect was observed than Gram-positive cells. The germicidal effect of TiO2 gradually decreased after exposure to air at room temperature, as the wetting property decreased. This kind of germicidal activity was more effective compared to other germicidal process such as UVA/TiO2 or Ag＋. This shed light on designing new germicidal material either maintained by visible light irradiation, or by oxidation effect generated by reactive oxygen species.展开更多
Glutathione S-transferases （GSTs） are phase II enzymes that facilitate the detoxification of xenobioties and play important roles in antioxidant defense. We investigated the expression patterns of seven Venerupis ph...Glutathione S-transferases （GSTs） are phase II enzymes that facilitate the detoxification of xenobioties and play important roles in antioxidant defense. We investigated the expression patterns of seven Venerupis philippinarum GSTs （VpGSTs） and four Mytilus galloprovincialis GSTs （MgGSTs） following exposure to BDE-47. Differential expressions of the seven VpGSTs and four MgGSTs transcripts were observed, with differences between the hepatopancreas and gills. Among these GSTs, the sigma classes （VpGSTS1, VpGSTS2, VpGSTS3, MgGST1, and MgGST3） were highly expressed in response to BDE-47 exposure, demonstrating their potential as molecular biomarkers for environmental biomonitoring studies. We obtained the three-dimensional crystal structures of VpGSTs and MgGSTs by homologous modeling. A model to elucidate the binding interactions between the ligands and receptors was defined by molecular docking, Hydrophobic and n were the most often observed interactions between BDE-47 and the GSTs.展开更多
Soil organic carbon(SOC)and nitrogen(N)are two of the most important indicators for agricultural productivity.The primary objective of this study was to investigate the changes in SOC and N in the deep soil profile(up...Soil organic carbon(SOC)and nitrogen(N)are two of the most important indicators for agricultural productivity.The primary objective of this study was to investigate the changes in SOC and N in the deep soil profile(up to 100 cm)and their relationships with crop productivity under the influence of long-term(since 1990)fertilization in the wheat-maize cropping system.Treatments included CK(control),NP(inorganic N and phosphorus(P)fertilizers),NPK(inorganic N,P and potassium fertilizers),NPKM(NPK plus manure),and M(manure).Crop yield and the properties of topsoil were measured yearly from 2001 to 2009.C and N contents were measured at five different depths in 2001 and 2009.The results showed that wheat and maize yields decreased between 2001 and 2009 under the inorganic fertilizer(NP and NPK)treatments.The average yield between 2001 and 2009 under the NP,NPK,NPKM,and M treatments(compared with the CK treatment)increased by 38,115,383,and 381%,respectively,for wheat and 348,891,2738,and 1845%,respectively,for maize.Different long-term fertilization treatments significantly changed coarse free particulate(cf POC),fine free particulate(ff POC),intramicroaggregate particulate(i POC),and mineral-associated(m SOC)organic carbon fractions.In the experimental years of 2001 and 2009,soil fractions occurred in the following order for all treatments:m SOC>cf POC>i POC>ff POC.All fractions were higher under the manure application treatments than under the inorganic fertilization treatments.Compared to the inorganic fertilization treatments,manure input enhanced the stocks of SOC and total N in the surface layer(0–20 cm)but decreased SOC and N in the deep soil layer(80–100 cm).This reveals the efficiency of manure in increasing yield productivity and decreasing risk of vertical loss of nutrients,especially N,compared to inorganic fertilization treatments.The findings provide opportunities for understanding deep soil C and N dynamics,which could help mitigate climate change impact on agricultural production and maintain soil health.展开更多
The reference values of serum perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations were evaluated based on the human blood samples collected from Kashi, Xinjiang. And human serum samples of fa...The reference values of serum perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations were evaluated based on the human blood samples collected from Kashi, Xinjiang. And human serum samples of family members from Liaoning were evaluated for levels of PFOS and PFOA with the purpose to compare exposure pathways for family members. Among the 110 blood specimens from Kashi, the detection frequency of PFOS and PFOA was 93% and 6%, respectively. Reference values of serum PFOS, evaluated as the 90th percentiles of the concentrations, were determined to be 6.44 μg/L. Significant positive correlations were observed for serum levels of PFOS and PFOA among family members in Liaoning. Specially, stronger correlation between mother and offspring was observed than that between father and offspring. And stronger correlation of serum PFOS and PFOA levels was observed among fam- ily members in rural areas than those in big and small-medium cities. Difference in the association of serum PFOS and PFOA level among family members suggested that exposure in the outdoor and working environment of different oc- cupations should be evaluated. Present study provides reference values for exposure assessment in China and potential pathways of human exposure to PFOS and PFOA.展开更多
In the present work,pulsed gas–liquid hybrid discharge plasma coupled with graphene/Cd S catalyst was evaluated to eliminate bisphenol A(BPA)in wastewater.The optimization of a series of process parameters was perfor...In the present work,pulsed gas–liquid hybrid discharge plasma coupled with graphene/Cd S catalyst was evaluated to eliminate bisphenol A(BPA)in wastewater.The optimization of a series of process parameters was performed in terms of BPA degradation performance.The experimental results demonstrated that nearly 90%of BPA(20 mg l^(-1))in the synthetic wastewater(p H=7.5,σ=10μS m^(-1))was degraded by the plasma catalytic system over 0.2 g l^(-1)graphene/Cd S at 19k V with a 4 l min^(-1)air flow rate and 10 mm electrode gap within 60 min.The BPA removal rate increased with increasing the discharge voltage and decreasing the initial BPA concentration or solution conductivity.Nevertheless,either too high or too low an air flow rate,electrode gap,catalyst dosage or initial solution p H would lead to a decrease in BPA degradation.Moreover,optical emission spectroscopy was used to gain information on short-lived reactive species formed from the pulsed gas–liquid hybrid discharge plasma system.The results indicated the existence of several highly oxidative free radicals such as·O and·OH.Finally,the activation pathway of O_(3)on the catalyst surface was analyzed by density functional theory.展开更多
The development of simple and accurate detection of uracil-DNA glycosylase(UDG)is of great significance for early clinical diagnosis and biomedical research.Here,we on the first effort introduced the uracil bases into...The development of simple and accurate detection of uracil-DNA glycosylase(UDG)is of great significance for early clinical diagnosis and biomedical research.Here,we on the first effort introduced the uracil bases into the rolling circle amplification(RCA)reaction to produce the functionalized pure DNA hydrogel(PDH)for UDG detection.During RCA process,methylene blue(MB)molecules as the indicators were encapsulated into PDH.The addition of UDG can remove the uracil bases of PDH to generate abasic sites,which are further cleaved with the assistance of apurinic/apyrimidinic endonuclease(APE),thus resulting in the dissociation of PDH to release blue MB.By combining with the paper analytical devices as the signal readout platform,a colorimetric and electrochemical dual-signal biosensor was constructed for convenient and accurate detection of UDG.The proposed MB@PDH-based dual-signal sensing system exhibited good selectivity and high sensitivity with a detection limit of 6.4104 U/mL(electrochemical method).It was also demonstrated that this sensing system showed excellent performance in UDG inhibitor screening,thus providing great potential in UDG-related disease diagnosis and drug discovery.展开更多
Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 a...Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 and CeO2 exhibit better activity and selectivity than pure Cu catalyst due to Cu-support(ZrO2 and CeO2)interaction.Combining the structural characterizations with in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS),Cu/CeO2 shows the higher methanol selectivity due to the formation of main carbonates intermediates,which are closely related with the oxygen vacancies over Cu/CeO2.In contrast,bicarbonate and carboxyl species are observed on Cu/ZrO2,which originates from the hydroxyl groups presented on catalyst surfaces.Difference in CO2 adsorption intermediates results in the distinct methanol selectivity over the two catalysts.展开更多
A series of CuO/Ce1-xZrxO2 catalysts(x=0.2,0.4,0.6 and 0.8)are applied to elaborate the effect of the Zr/Ce ratio on the catalytic performance of CO2 hydrogenation to CH3OH.The best catalytic performance is achieved w...A series of CuO/Ce1-xZrxO2 catalysts(x=0.2,0.4,0.6 and 0.8)are applied to elaborate the effect of the Zr/Ce ratio on the catalytic performance of CO2 hydrogenation to CH3OH.The best catalytic performance is achieved with CuO/Ce0.4Zr0.6O2,exhibiting XCO2=13.2%and YCH3OH=9.47%(T=280℃,P=3 MPa).The formation of dispersed surface CuO species and larger number of oxygen vacancies are detected over CuO/Ce0.4Zr0.6O2 due to stronger interaction between CuO and Ce0.4Zr0.6O2,resulting in the superior activation ability for H2 and CO2 respectively.Additionally,the evidence is provided by in situ DRIFTS under the activity test pressure(3 MPa)that bi/m-HCOO* species are preferable for accumulating over ceria-rich(CuO/Ce0.6Zr0.4O2 and CuO/Ce0.8Zr0.2O2)catalysts while zirconia-rich(CuO/Ce0.4Zr0.6O2 and CuO/Ce0.2Zr0.8O2)catalysts are benefit to encourage the transformation of bi/m-HCOO* species to CH3OH.The abundant population and high activity of intermediate species over CuO/Ce0.4Zr0.6O2 give a strong positive effect on the catalytic performance.展开更多
In this work, a novel gas phase silent-packed bed hybrid discharge plasma reactor has been proposed, and its ability to control a simulative gas stream containing 240 ppm benzene is experimentally investigated. In ord...In this work, a novel gas phase silent-packed bed hybrid discharge plasma reactor has been proposed, and its ability to control a simulative gas stream containing 240 ppm benzene is experimentally investigated. In order to optimize the geometry of the reactor, the benzene conversion rate and energy yield （EY） were compared for various inner electrode diameters and quartz tube shapes and sizes. In addition, benzene removal efficiency in different discharge regions was qualitatively analyzed and the gas parameter （space velocity） was systematically studied. It has been found that silent-packed bed hybrid discharge plasma reactor can effectively decompose benzene. Benzene removal proved to achieve an optimum value of 60% with a characteristic energy density of 255 J/L in this paper with a 6 mm bolt high-voltage electrode and a 13 mm quartz tube. The optimal space velocity was 188.1 h^-1, which resulted in moderate energy yield and removal efficiency. Reaction by-products such as hydroquinone, heptanoic acid, 4-nitrocatechol, phenol and 4-phenoxy-phenol were identified by mean of GC-MS. In addition, based on these organic by-products, a benzene destruction pathway was proposed.展开更多
The catalytic oxidation of toluene over Ag/SBA‐15synthesized under different pretreatment conditions,including O2at500°C(denoted O500),H2at500°C(H500),and O2at500°C followed by H2at300°C(O500‐H30...The catalytic oxidation of toluene over Ag/SBA‐15synthesized under different pretreatment conditions,including O2at500°C(denoted O500),H2at500°C(H500),and O2at500°C followed by H2at300°C(O500‐H300)was studied.The pretreated samples were investigated by N2physisorption,X‐ray diffraction,and ultraviolet‐visible diffuse reflectance.The pretreatment atmosphere greatly influences the status of the Ag and O species,which in turn significantly impacts the adsorption and catalytic removal of toluene.Ag2O and amorphous Ag particles,as well as a large amount of subsurface oxygen species,are formed on O500,and the subsurface oxygen enhances the interaction between Ag species and toluene,so O500shows good activity at higher temperature.However,its activity at lower temperature is not as high as expected,with a reduced presence of Ag2O and lower adsorption capacity for toluene.H2pretreatment at500°C is conducive to the formation of large Ag particles and yields the largest adsorption capacity for toluene,so H500exhibits the best activity at lower temperatures;however,because of poor interaction between Ag and toluene,its activity at higher temperature is modest.The O500‐H300sample exhibits excellent catalytic activity during the whole reaction process,which can be attributed to the small and highly dispersed Ag nanoparticles as well as the existence of subsurface oxygen.展开更多
Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped t...Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped to the external wall （used as ground electrode）, was introduced to generate active species which were sprayed into the organic solution through an aerator fixed on the bottom of the tube. The effect of four factors-the discharge voltage, gas flow rate, solution conductivity, and pH of wastewater, on the degradation efficiency of phenol was assessed. The obtained results demonstrated that this process was an effective method for phenol degradation. The degradation rate was enhanced with the increase in power supplied. The degradation efficiency in alkaline conditions was higher than those in acid and neutral conditions. The optimal gas flow rate for phenol degradation in the system was 1.6 L/min, while the solution conductivity had little effect on the degradation.展开更多
In this study, dielectric barrier discharge plasma and ozone(O_3) were combined to synergistically degrade trans-ferulic acid(FA), and the effect of water quality on FA degradation was studied. The results showed that...In this study, dielectric barrier discharge plasma and ozone(O_3) were combined to synergistically degrade trans-ferulic acid(FA), and the effect of water quality on FA degradation was studied. The results showed that 96.9% of FA was degraded after 40 min treatment by the plasma/O_3 process. FA degradation efficiency increased with the p H values. The presence of suspended solid and humic acid inhibited FA degradation. FA degradation efficiency increased as the water temperature increased to 30 °C. However, the further increase in water temperature was adverse for FA degradation. Effects of common inorganic ions on FA degradation were also investigated. The addition of Cl^- inhibited the FA degradation, whileCO_3^(2-) had both negative and positive influences on FA degradation.NO_3^- andSO_4^(2-) did not have significant effect on FA degradation. Fe^(3+)and Cu^(2+)benefited FA degradation through the Fenton-like and catalytic ozonation reactions.展开更多
Photodegradation ofpentachlorophenol （PCP） and p-nitrophenol （PNP） in soil was carried out in a designed rotary reactor, which can provide the soil particles with continually uniform irradiation, and on a series o...Photodegradation ofpentachlorophenol （PCP） and p-nitrophenol （PNP） in soil was carried out in a designed rotary reactor, which can provide the soil particles with continually uniform irradiation, and on a series of thin soil layers. TiO2, as a kind of environmental friendly photocatalyst, was introduced to the soil to enhance the processes. Compared with that on the soil layers, photodegradation of PCP at initial concentration of 60 mg/kg was improved dramatically in the rotary reactor no matter whether TiO2 was added, with an increase of 3.0 times in the apparent first-order rate constants. The addition of 1 wt% TiO2 furthered the improvement by 1.4 times. Without addition of TiO2, PNP （initial concentration of 60 mg/kg） photodegradation rate in the rotary reactor was similar to that on the soil layers. When 1 wt% additional TiO2 was added, PNP photodegradation was enhanced obviously, and the enhancement in the rotary reactor was 2 times of that on the soil layers, which may be attributed to the higher frequency of the contact between PNP on soil particles and the photocatalyst. The effect of soil pH and initial concentrations of the target compounds on the photodegradation in the rotary reactor was investigated. The order of the degradation rate at different soil pH was relative to the aggregation of soil particles during mixing in the rotary reactor. Photodegradation of PCP and PNP at different initial concentrations showed that addition of TiO2 to enhance the photodegradation was more suitable for contaminated soil with higher concentration of PCP, while was effective for contaminated soil at each PNP concentration tested in our study.展开更多
Designing effective catalyst to improve the activity of CO_(2) hydrogenation to methanol is a potential avenue to realize the utilization of CO_(2) resources. Herein we construct three kinds of Cu/Ce_(x)Zr_(y)O_(z)(CC...Designing effective catalyst to improve the activity of CO_(2) hydrogenation to methanol is a potential avenue to realize the utilization of CO_(2) resources. Herein we construct three kinds of Cu/Ce_(x)Zr_(y)O_(z)(CCZ) catalysts with different crystal phases of Ce_(x)Zr_(y)O_(z)solid solutions, which demonstrate distinct activity and methanol selectivity in the order of metastable tetragonal-CCZ(CCZ-t’’, parts of oxygen in Ce_(x)Zr_(y)O_(z) were replaced by tetragonal phase from cubic fluorite phase) > tetragonal-CCZ(CCZ-t) > cubic-CCZ(CCZ-c) for CO_(2) hydrogenation to methanol. Structural analysis reveals that oxygen vacancies, surface hydroxyls and unsaturated Cu species of CCZ all follow the same sequence as that of activity and methanol selectivity,indicating that the above features are beneficial to improve the catalytic reaction performance.Temperature programmed experiments and mechanism studies show that the interface between Cu and tetragonal(t and t’’) Ce_(x)Zr_(y)O_(z) can promote CO_(2) adsorption, and the adsorbed CO_(2) is more reactive and can generate active bidentate carbonate species, which can be hydrogenated to form active monodentate and bidentate formate species under CO_(2) and H_(2) atmosphere. These intermediates should be crucial to the formation of methanol product. CCZ-t’’has stronger H_(2) activation ability than CCZ-t, which makes the former catalyst have more intermediates and higher methanol selectivity. In contrast, CO_(2) mainly adsorbs on cubic Ce_(x)Zr_(y)O_(z) support of CCZ-c, but its H_(2) spillover ability is low, which hinders the reaction process. In addition, the strong adsorption of surface intermediates on CCZ-c is also not conducive to methanol formation. Results here demonstrate that constructing active Cu-support interfaces may be an important approach to design effective catalyst for CO_(2)hydrogenation.展开更多
In the present study,a combination of pulsed discharge plasma and TiO2（plasma/TiO2）has been developed in order to study the activity of TiO2by varying the discharge conditions of pulsed voltage,discharge mode,air fl...In the present study,a combination of pulsed discharge plasma and TiO2（plasma/TiO2）has been developed in order to study the activity of TiO2by varying the discharge conditions of pulsed voltage,discharge mode,air flow rate and solution conductivity.Phenol was used as the chemical probe to characterize the activity of TiO2in a pulsed discharge system.The experimental results showed that the phenol removal efficiency could be improved by about 10%by increasing the applied voltage.The phenol removal efficiency for three discharge modes in the plasma-discharge-alone system was found to be highest in the spark mode,followed by the spark–streamer mode and finally the streamer mode.In the plasma/TiO2system,the highest catalytic effect of TiO2was observed in the spark–streamer discharge mode,which may be attributed to the favorable chemical and physical effects from the spark–streamer discharge mode,such as ultraviolet light,O3,H2O2,pyrolysis,shockwaves and high-energy electrons.Meanwhile,the optimal flow rate and conductivity were 0.05 m^3l^（-1）and 10μS cm^（-1）,respectively.The main phenolic intermediates were hydroquinone,catechol,and p-benzoquinone during the discharge treatment process.A different phenol degradation pathway was observed in the plasma/TiO2system as compared to plasma alone.Analysis of the reaction intermediates demonstrated that p-benzoquinone reduction was selectively catalyzed on the TiO2surface.The effective decomposition of phenol constant（De）increased from 74.11%to 79.16%when TiO2was added,indicating that higher phenol mineralization was achieved in the plasma/TiO2system.展开更多
Due to the deterioration of serious energy dilemma,energy-conservation and emission–reduction have been the strategic target in the past decades,thus people have identified the vital importance of higher energy effic...Due to the deterioration of serious energy dilemma,energy-conservation and emission–reduction have been the strategic target in the past decades,thus people have identified the vital importance of higher energy efficiency and the influence of lower carbon development.Since work exchange network is a significant part of energy recovery system,its optima design will have dramatically significant effect on energy consumption reduction in chemical process system.With an extension of the developed transshipment model in isothermal process,a novel step-wise methodology for synthesis of direct work exchange network(WEN)in adiabatic process involving heat integration is first proposed in this paper,where a nonlinear programming(NLP)model is formulated by regarding the minimum utility consumption as objective function and optimizing the initial WEN in accordance with the presented matching rules to get the optimized WEN configuration at first.Furthermore,we focus on the work exchange network synthesis with heat integration to attain the minimal total annual cost(TAC)with the introduction of heat-exchange equipment that is achieved by the following strategies in sequence:introducing heat-exchange equipment directly,adjusting the work quantity of the adjacent utility compressors or expanders,and approximating upper/lower pressure limits consequently to obtain considerable cost savings of expanders or compressors and work utility.Finally,a case taken from the literature is studied to illustrate the feasibility and effectiveness of the proposed method.展开更多
文摘Thermal decomposition of polylactic acid （PLA） was studied in the presence of pine wood sawdust （PS）, walnut shell （WS）, corncob （CC） in order to understand the pyrolytic behavior of these components occurring in waste. A thermogravimetric analyzer （TGA） was applied for monitoring the mass loss profiles under heating rate of 10℃·min^-1. Results obtained from this comprehensive investigation indicated that PLA was decomposed in the temperature range 300 -372℃, whereas the thermal degradation temperature of biomass is 183-462℃. The difference of mass loss （AW） between experimental and theoretical ones, calculated as algebraic sums of those from each separated component, is about 17%-46% at 300-400℃. These experimental results indicated a significant synergistic effect during PLA and biomass copyrolysis. Moreover, a kinetic analysis was performed to fit thermogravimetric data, the global processes being considered as one to two consecutive reactions. A reasonable fit to the experimental data was obtained for all materials and their blends.
基金supported by the Specialized Research Fund for Sanjin Scholars Program of Shanxi Province(201707)Key Research&Development Plan of Shanxi Province(201903D321059)+2 种基金Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province(20200004)Transformation and Cultivation Projects of Scientific and Technological Achievements in Universities of Shanxi Province Institutions(2020CG040)the China National Key Project of Science and Technology “Major Science and Technology Program for Water Pollution Control and Treatment”(2018ZX07601001)。
文摘This study investigated catalytic decomposition and mass transfer of aqueous ozone promoted by Fe-MnCu/γ-Al_(2)O_(3)(Cat)in a rotating packed bed(RPB)for the first time.The results showed that the value of the overall decomposition rate constant of ozone(K_(c))and overall volumetric mass transfer coefficient(K_(L)a)are 4.28×10^(-3) s^(-1) and 11.60×10^(-3) s^(-1) respectively at an initial pH of 6,βof 40,Co3(g)of 60 mg·L^(-1)and Q_(L) of 85 L·h^(-1) in deionized water,respectively.Meanwhile,the K_(c) and K_(L)a values of Fenhe water are0.88×10^(-3) s^(-1) and 2.51×10^(-3) s^(-1) lower than deionized water,respectively.In addition,the K_(c) and K_(L)a values in deionized water for the Cat/O_(3)-RPB system are 44.86%and 47.41%higher than that for the Cat/O_(3)-BR(bubbling reactor)system,respectively,indicating that the high gravity technology can facilitate the decomposition and mass transfer of ozone in heterogeneous catalytic ozonation and provide some insights into the industrial wastewater.
基金supported financially by the Program for New Century Excellent Talents in University (NCET-09-0256)the Fundamental Research Funds for the Central Universities (DUT13LK27)the National Nature Science Foundation of China (No.21377016)
文摘CO and formaldehyde(HCHO)oxidation reactions were investigated over mesoporous Ag/Co3O4 catalysts prepared by one-pot(OP)and impregnation(IM)methods.It was found that the one-pot method was superior to the impregnation method for synthesizing Ag/Co3O4 catalysts with high activity for both reactions.It was also found that the catalytic behavior of mesoporous Co3O4 and Ag/Co3O4 catalysts for the both reactions was different.And the addition of silver on mesoporous Co3O4 did not always enhance the catalytic activity of final catalyst for CO oxidation at room temperature(20 C),but could significantly improve the catalytic activity of final catalyst for HCHO oxidation at low temperature(90 C).The high surface area,uniform pore structure and the pretty good dispersion degree of the silver particle should be responsible for the excellent low-temperature CO oxidation activity.However,for HCHO oxidation,the addition of silver played an important role in the activity enhancement.And the silver particle size and the reducibility of Co3O4 should be indispensable for the high activity of HCHO oxidation at low temperature.
基金supported by the National Key Research and Development Program of China(2016YFD0300901)the Fundamental Research Funds for Central Nonprofit Scientific Institutions of China(1610132019035,1610132020023 and 1610132020024)the Natural Science Foundation of Jiangxi Province,China(20192BAB203022)。
文摘Understanding the impact of biological activities on the soil phosphorus(P)distribution under long-term fertilizer application can facilitate better soil P fertility management.Therefore,the primary objectives of this study were to investigate the effect of long-term(since 1981)fertilizer application on the soil P fractions and microbial community and to evaluate correlations between the microbial community structure and P distribution.The following treatments were implemented in a long-term field trial:no fertilization(CK),inorganic N and K(NK),inorganic P and K(PK),inorganic N,P and K(NPK)and manure+NPK(MNPK)fertilization.The study showed that the soil pH,soil organic carbon and total and available N and P concentrations were considerably higher in the MNPK treatment than in the CK treatment.The soil microbial biomass C,N and P concentrations were also significantly higher in the MNPK treatment than in the CK treatment.Among fertilization treatments,theβ-1,4-glucosidase,α-1,4-glucosidase,urease,acid phosphatase and phosphodiesterase activities were the highest in the MNPK treatment.Compared to inorganic fertilization,the MNPK treatment increased the labile soil P fractions and decreased the residual soil P concentration.Continuous fertilization significantly affected the soil microbial composition.The total phospholipid fatty acid(PLFA)concentrations in the NK,PK,NPK and MNPK treatments were 23.3,43.1,48.7 and 87.7%higher,respectively,than in the CK treatment.A significant correlation was observed between the microbial community and soil P fractions.Moreover,the aggregated boosted tree(ABT)model showed that among the various soil biochemical properties,the total PLFA concentration was the factor that most influenced the active P pool,accounting for 35.4%of the relative influence of all soil biochemical properties examined.These findings reveal that combined manure and inorganic fertilizer application is a better approach than applying inorganic fertilizer alone for sustaining long-term P fertility by mediating soil biological activity.
基金the support and funding from Innovation Technology Foundation from Hong Kong SAR.
文摘Fresh TiO2 was found to possess a strong germicidal activity even without UV irradiation. Live Yeast （Saccharomyces cerevisiae） cells in contact with fresh TiO2 were found deformed and dead after 15min contact. The cause of germicidal activity was discussed from the observed cell deformation, lysis and increased absorption at 1680 cm^-1 in FT-IR spectra of the affected cells, which proved the oxidizing effect of fresh TiO2 to cells. The deformation caused by the stretching of cell wail and pressure built-up inside the cell, led to cell burst and release of intracellular materials. The degree of cell deformation was found positively related with the wetting property of TiO2. Cells are negatively charged, for Gram-negative cell （thinner ceil wail）, a higher germicidal effect was observed than Gram-positive cells. The germicidal effect of TiO2 gradually decreased after exposure to air at room temperature, as the wetting property decreased. This kind of germicidal activity was more effective compared to other germicidal process such as UVA/TiO2 or Ag＋. This shed light on designing new germicidal material either maintained by visible light irradiation, or by oxidation effect generated by reactive oxygen species.
基金Supported by the National Natural Science Foundation of China(No.21107136)the International Foundation for Science(No.F/5230-1)
文摘Glutathione S-transferases （GSTs） are phase II enzymes that facilitate the detoxification of xenobioties and play important roles in antioxidant defense. We investigated the expression patterns of seven Venerupis philippinarum GSTs （VpGSTs） and four Mytilus galloprovincialis GSTs （MgGSTs） following exposure to BDE-47. Differential expressions of the seven VpGSTs and four MgGSTs transcripts were observed, with differences between the hepatopancreas and gills. Among these GSTs, the sigma classes （VpGSTS1, VpGSTS2, VpGSTS3, MgGST1, and MgGST3） were highly expressed in response to BDE-47 exposure, demonstrating their potential as molecular biomarkers for environmental biomonitoring studies. We obtained the three-dimensional crystal structures of VpGSTs and MgGSTs by homologous modeling. A model to elucidate the binding interactions between the ligands and receptors was defined by molecular docking, Hydrophobic and n were the most often observed interactions between BDE-47 and the GSTs.
基金financially supported by the National Key Research and Development Program of China(2016YFD0300901 and 2017YFD0800101)the Fundamental Research Funds for Central Non-profit Scientific Institution,China(161032019035,1610132020022 and 1610132020023)。
文摘Soil organic carbon(SOC)and nitrogen(N)are two of the most important indicators for agricultural productivity.The primary objective of this study was to investigate the changes in SOC and N in the deep soil profile(up to 100 cm)and their relationships with crop productivity under the influence of long-term(since 1990)fertilization in the wheat-maize cropping system.Treatments included CK(control),NP(inorganic N and phosphorus(P)fertilizers),NPK(inorganic N,P and potassium fertilizers),NPKM(NPK plus manure),and M(manure).Crop yield and the properties of topsoil were measured yearly from 2001 to 2009.C and N contents were measured at five different depths in 2001 and 2009.The results showed that wheat and maize yields decreased between 2001 and 2009 under the inorganic fertilizer(NP and NPK)treatments.The average yield between 2001 and 2009 under the NP,NPK,NPKM,and M treatments(compared with the CK treatment)increased by 38,115,383,and 381%,respectively,for wheat and 348,891,2738,and 1845%,respectively,for maize.Different long-term fertilization treatments significantly changed coarse free particulate(cf POC),fine free particulate(ff POC),intramicroaggregate particulate(i POC),and mineral-associated(m SOC)organic carbon fractions.In the experimental years of 2001 and 2009,soil fractions occurred in the following order for all treatments:m SOC>cf POC>i POC>ff POC.All fractions were higher under the manure application treatments than under the inorganic fertilization treatments.Compared to the inorganic fertilization treatments,manure input enhanced the stocks of SOC and total N in the surface layer(0–20 cm)but decreased SOC and N in the deep soil layer(80–100 cm).This reveals the efficiency of manure in increasing yield productivity and decreasing risk of vertical loss of nutrients,especially N,compared to inorganic fertilization treatments.The findings provide opportunities for understanding deep soil C and N dynamics,which could help mitigate climate change impact on agricultural production and maintain soil health.
文摘The reference values of serum perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations were evaluated based on the human blood samples collected from Kashi, Xinjiang. And human serum samples of family members from Liaoning were evaluated for levels of PFOS and PFOA with the purpose to compare exposure pathways for family members. Among the 110 blood specimens from Kashi, the detection frequency of PFOS and PFOA was 93% and 6%, respectively. Reference values of serum PFOS, evaluated as the 90th percentiles of the concentrations, were determined to be 6.44 μg/L. Significant positive correlations were observed for serum levels of PFOS and PFOA among family members in Liaoning. Specially, stronger correlation between mother and offspring was observed than that between father and offspring. And stronger correlation of serum PFOS and PFOA levels was observed among fam- ily members in rural areas than those in big and small-medium cities. Difference in the association of serum PFOS and PFOA level among family members suggested that exposure in the outdoor and working environment of different oc- cupations should be evaluated. Present study provides reference values for exposure assessment in China and potential pathways of human exposure to PFOS and PFOA.
基金supported by the Open Fund for State Environmental Protection Key Laboratory of Synergetic Control and Joint Remediation for Soil&Water Pollution(No.GHBK-2020-006)National Natural Science Foundation of China(No.21876070)。
文摘In the present work,pulsed gas–liquid hybrid discharge plasma coupled with graphene/Cd S catalyst was evaluated to eliminate bisphenol A(BPA)in wastewater.The optimization of a series of process parameters was performed in terms of BPA degradation performance.The experimental results demonstrated that nearly 90%of BPA(20 mg l^(-1))in the synthetic wastewater(p H=7.5,σ=10μS m^(-1))was degraded by the plasma catalytic system over 0.2 g l^(-1)graphene/Cd S at 19k V with a 4 l min^(-1)air flow rate and 10 mm electrode gap within 60 min.The BPA removal rate increased with increasing the discharge voltage and decreasing the initial BPA concentration or solution conductivity.Nevertheless,either too high or too low an air flow rate,electrode gap,catalyst dosage or initial solution p H would lead to a decrease in BPA degradation.Moreover,optical emission spectroscopy was used to gain information on short-lived reactive species formed from the pulsed gas–liquid hybrid discharge plasma system.The results indicated the existence of several highly oxidative free radicals such as·O and·OH.Finally,the activation pathway of O_(3)on the catalyst surface was analyzed by density functional theory.
基金supported by the National Natural Science Foundation of China(NSFC,Grant No.21922601).
文摘The development of simple and accurate detection of uracil-DNA glycosylase(UDG)is of great significance for early clinical diagnosis and biomedical research.Here,we on the first effort introduced the uracil bases into the rolling circle amplification(RCA)reaction to produce the functionalized pure DNA hydrogel(PDH)for UDG detection.During RCA process,methylene blue(MB)molecules as the indicators were encapsulated into PDH.The addition of UDG can remove the uracil bases of PDH to generate abasic sites,which are further cleaved with the assistance of apurinic/apyrimidinic endonuclease(APE),thus resulting in the dissociation of PDH to release blue MB.By combining with the paper analytical devices as the signal readout platform,a colorimetric and electrochemical dual-signal biosensor was constructed for convenient and accurate detection of UDG.The proposed MB@PDH-based dual-signal sensing system exhibited good selectivity and high sensitivity with a detection limit of 6.4104 U/mL(electrochemical method).It was also demonstrated that this sensing system showed excellent performance in UDG inhibitor screening,thus providing great potential in UDG-related disease diagnosis and drug discovery.
基金financially supported by the National Natural Science Foundation of China (21577014, 21876019, 21825203, 21688102)Programme of Introducing Talents of Discipline to Universities (B13012)the fund of the State Key Laboratory of Catalysis in DICP (Y401010502)
文摘Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 and CeO2 exhibit better activity and selectivity than pure Cu catalyst due to Cu-support(ZrO2 and CeO2)interaction.Combining the structural characterizations with in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS),Cu/CeO2 shows the higher methanol selectivity due to the formation of main carbonates intermediates,which are closely related with the oxygen vacancies over Cu/CeO2.In contrast,bicarbonate and carboxyl species are observed on Cu/ZrO2,which originates from the hydroxyl groups presented on catalyst surfaces.Difference in CO2 adsorption intermediates results in the distinct methanol selectivity over the two catalysts.
基金financially supported by the National Nature Science Foundation of China (21876019, 21577014)Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020000)the fund of the State Key Laboratory of Catalysis in DICP (N18-08)。
文摘A series of CuO/Ce1-xZrxO2 catalysts(x=0.2,0.4,0.6 and 0.8)are applied to elaborate the effect of the Zr/Ce ratio on the catalytic performance of CO2 hydrogenation to CH3OH.The best catalytic performance is achieved with CuO/Ce0.4Zr0.6O2,exhibiting XCO2=13.2%and YCH3OH=9.47%(T=280℃,P=3 MPa).The formation of dispersed surface CuO species and larger number of oxygen vacancies are detected over CuO/Ce0.4Zr0.6O2 due to stronger interaction between CuO and Ce0.4Zr0.6O2,resulting in the superior activation ability for H2 and CO2 respectively.Additionally,the evidence is provided by in situ DRIFTS under the activity test pressure(3 MPa)that bi/m-HCOO* species are preferable for accumulating over ceria-rich(CuO/Ce0.6Zr0.4O2 and CuO/Ce0.8Zr0.2O2)catalysts while zirconia-rich(CuO/Ce0.4Zr0.6O2 and CuO/Ce0.2Zr0.8O2)catalysts are benefit to encourage the transformation of bi/m-HCOO* species to CH3OH.The abundant population and high activity of intermediate species over CuO/Ce0.4Zr0.6O2 give a strong positive effect on the catalytic performance.
基金supported by the Program for National Natural Science Foundation of China (No.51177007)Liaoning Excellent Talents in University of China (Project No.2009R09)863 Program of China (No.2009AA064101-4)
文摘In this work, a novel gas phase silent-packed bed hybrid discharge plasma reactor has been proposed, and its ability to control a simulative gas stream containing 240 ppm benzene is experimentally investigated. In order to optimize the geometry of the reactor, the benzene conversion rate and energy yield （EY） were compared for various inner electrode diameters and quartz tube shapes and sizes. In addition, benzene removal efficiency in different discharge regions was qualitatively analyzed and the gas parameter （space velocity） was systematically studied. It has been found that silent-packed bed hybrid discharge plasma reactor can effectively decompose benzene. Benzene removal proved to achieve an optimum value of 60% with a characteristic energy density of 255 J/L in this paper with a 6 mm bolt high-voltage electrode and a 13 mm quartz tube. The optimal space velocity was 188.1 h^-1, which resulted in moderate energy yield and removal efficiency. Reaction by-products such as hydroquinone, heptanoic acid, 4-nitrocatechol, phenol and 4-phenoxy-phenol were identified by mean of GC-MS. In addition, based on these organic by-products, a benzene destruction pathway was proposed.
基金supported by the National Natural Science Foundation of China(21377016,21577014)Program for Changjiang Scholars and Innovative Research Team in University(IRT_13R05)~~
文摘The catalytic oxidation of toluene over Ag/SBA‐15synthesized under different pretreatment conditions,including O2at500°C(denoted O500),H2at500°C(H500),and O2at500°C followed by H2at300°C(O500‐H300)was studied.The pretreated samples were investigated by N2physisorption,X‐ray diffraction,and ultraviolet‐visible diffuse reflectance.The pretreatment atmosphere greatly influences the status of the Ag and O species,which in turn significantly impacts the adsorption and catalytic removal of toluene.Ag2O and amorphous Ag particles,as well as a large amount of subsurface oxygen species,are formed on O500,and the subsurface oxygen enhances the interaction between Ag species and toluene,so O500shows good activity at higher temperature.However,its activity at lower temperature is not as high as expected,with a reduced presence of Ag2O and lower adsorption capacity for toluene.H2pretreatment at500°C is conducive to the formation of large Ag particles and yields the largest adsorption capacity for toluene,so H500exhibits the best activity at lower temperatures;however,because of poor interaction between Ag and toluene,its activity at higher temperature is modest.The O500‐H300sample exhibits excellent catalytic activity during the whole reaction process,which can be attributed to the small and highly dispersed Ag nanoparticles as well as the existence of subsurface oxygen.
基金supported by Ministry of Education of the People's Republic of China (20070141004)
文摘Investigation was made into the degradation of organic compounds by a dielectric barrier corona discharge （DBCD） system. The DBCD, consisting of a quartz tube, a concentric high voltage electrode and a net wrapped to the external wall （used as ground electrode）, was introduced to generate active species which were sprayed into the organic solution through an aerator fixed on the bottom of the tube. The effect of four factors-the discharge voltage, gas flow rate, solution conductivity, and pH of wastewater, on the degradation efficiency of phenol was assessed. The obtained results demonstrated that this process was an effective method for phenol degradation. The degradation rate was enhanced with the increase in power supplied. The degradation efficiency in alkaline conditions was higher than those in acid and neutral conditions. The optimal gas flow rate for phenol degradation in the system was 1.6 L/min, while the solution conductivity had little effect on the degradation.
文摘In this study, dielectric barrier discharge plasma and ozone(O_3) were combined to synergistically degrade trans-ferulic acid(FA), and the effect of water quality on FA degradation was studied. The results showed that 96.9% of FA was degraded after 40 min treatment by the plasma/O_3 process. FA degradation efficiency increased with the p H values. The presence of suspended solid and humic acid inhibited FA degradation. FA degradation efficiency increased as the water temperature increased to 30 °C. However, the further increase in water temperature was adverse for FA degradation. Effects of common inorganic ions on FA degradation were also investigated. The addition of Cl^- inhibited the FA degradation, whileCO_3^(2-) had both negative and positive influences on FA degradation.NO_3^- andSO_4^(2-) did not have significant effect on FA degradation. Fe^(3+)and Cu^(2+)benefited FA degradation through the Fenton-like and catalytic ozonation reactions.
基金The National Basic Research Program of China (No. 2004CB418504 2003CB415006)
文摘Photodegradation ofpentachlorophenol （PCP） and p-nitrophenol （PNP） in soil was carried out in a designed rotary reactor, which can provide the soil particles with continually uniform irradiation, and on a series of thin soil layers. TiO2, as a kind of environmental friendly photocatalyst, was introduced to the soil to enhance the processes. Compared with that on the soil layers, photodegradation of PCP at initial concentration of 60 mg/kg was improved dramatically in the rotary reactor no matter whether TiO2 was added, with an increase of 3.0 times in the apparent first-order rate constants. The addition of 1 wt% TiO2 furthered the improvement by 1.4 times. Without addition of TiO2, PNP （initial concentration of 60 mg/kg） photodegradation rate in the rotary reactor was similar to that on the soil layers. When 1 wt% additional TiO2 was added, PNP photodegradation was enhanced obviously, and the enhancement in the rotary reactor was 2 times of that on the soil layers, which may be attributed to the higher frequency of the contact between PNP on soil particles and the photocatalyst. The effect of soil pH and initial concentrations of the target compounds on the photodegradation in the rotary reactor was investigated. The order of the degradation rate at different soil pH was relative to the aggregation of soil particles during mixing in the rotary reactor. Photodegradation of PCP and PNP at different initial concentrations showed that addition of TiO2 to enhance the photodegradation was more suitable for contaminated soil with higher concentration of PCP, while was effective for contaminated soil at each PNP concentration tested in our study.
基金supported by the National Key Research and Development Program of China (2019YFC1903903)the National Natural Science Foundation of China (21876019, 21806017)+2 种基金the Dalian Science and Technology Innovation Fund (2019J12SN74)the China Postdoctoral Science Foundation (2020M680953)the funds of the State Key Laboratory of Catalysis in DICP (N-18-08, N-20-04)。
文摘Designing effective catalyst to improve the activity of CO_(2) hydrogenation to methanol is a potential avenue to realize the utilization of CO_(2) resources. Herein we construct three kinds of Cu/Ce_(x)Zr_(y)O_(z)(CCZ) catalysts with different crystal phases of Ce_(x)Zr_(y)O_(z)solid solutions, which demonstrate distinct activity and methanol selectivity in the order of metastable tetragonal-CCZ(CCZ-t’’, parts of oxygen in Ce_(x)Zr_(y)O_(z) were replaced by tetragonal phase from cubic fluorite phase) > tetragonal-CCZ(CCZ-t) > cubic-CCZ(CCZ-c) for CO_(2) hydrogenation to methanol. Structural analysis reveals that oxygen vacancies, surface hydroxyls and unsaturated Cu species of CCZ all follow the same sequence as that of activity and methanol selectivity,indicating that the above features are beneficial to improve the catalytic reaction performance.Temperature programmed experiments and mechanism studies show that the interface between Cu and tetragonal(t and t’’) Ce_(x)Zr_(y)O_(z) can promote CO_(2) adsorption, and the adsorbed CO_(2) is more reactive and can generate active bidentate carbonate species, which can be hydrogenated to form active monodentate and bidentate formate species under CO_(2) and H_(2) atmosphere. These intermediates should be crucial to the formation of methanol product. CCZ-t’’has stronger H_(2) activation ability than CCZ-t, which makes the former catalyst have more intermediates and higher methanol selectivity. In contrast, CO_(2) mainly adsorbs on cubic Ce_(x)Zr_(y)O_(z) support of CCZ-c, but its H_(2) spillover ability is low, which hinders the reaction process. In addition, the strong adsorption of surface intermediates on CCZ-c is also not conducive to methanol formation. Results here demonstrate that constructing active Cu-support interfaces may be an important approach to design effective catalyst for CO_(2)hydrogenation.
基金funded by the Fundamental Research Funds for the Central Universities under Grant(DUT 15QY17)National Natural Science Foundation of China(Project Nos.51477025 and U1462105)
文摘In the present study,a combination of pulsed discharge plasma and TiO2（plasma/TiO2）has been developed in order to study the activity of TiO2by varying the discharge conditions of pulsed voltage,discharge mode,air flow rate and solution conductivity.Phenol was used as the chemical probe to characterize the activity of TiO2in a pulsed discharge system.The experimental results showed that the phenol removal efficiency could be improved by about 10%by increasing the applied voltage.The phenol removal efficiency for three discharge modes in the plasma-discharge-alone system was found to be highest in the spark mode,followed by the spark–streamer mode and finally the streamer mode.In the plasma/TiO2system,the highest catalytic effect of TiO2was observed in the spark–streamer discharge mode,which may be attributed to the favorable chemical and physical effects from the spark–streamer discharge mode,such as ultraviolet light,O3,H2O2,pyrolysis,shockwaves and high-energy electrons.Meanwhile,the optimal flow rate and conductivity were 0.05 m^3l^（-1）and 10μS cm^（-1）,respectively.The main phenolic intermediates were hydroquinone,catechol,and p-benzoquinone during the discharge treatment process.A different phenol degradation pathway was observed in the plasma/TiO2system as compared to plasma alone.Analysis of the reaction intermediates demonstrated that p-benzoquinone reduction was selectively catalyzed on the TiO2surface.The effective decomposition of phenol constant（De）increased from 74.11%to 79.16%when TiO2was added,indicating that higher phenol mineralization was achieved in the plasma/TiO2system.
基金Supported by the National Natural Science Foundation of China(21576036,21406026)
文摘Due to the deterioration of serious energy dilemma,energy-conservation and emission–reduction have been the strategic target in the past decades,thus people have identified the vital importance of higher energy efficiency and the influence of lower carbon development.Since work exchange network is a significant part of energy recovery system,its optima design will have dramatically significant effect on energy consumption reduction in chemical process system.With an extension of the developed transshipment model in isothermal process,a novel step-wise methodology for synthesis of direct work exchange network(WEN)in adiabatic process involving heat integration is first proposed in this paper,where a nonlinear programming(NLP)model is formulated by regarding the minimum utility consumption as objective function and optimizing the initial WEN in accordance with the presented matching rules to get the optimized WEN configuration at first.Furthermore,we focus on the work exchange network synthesis with heat integration to attain the minimal total annual cost(TAC)with the introduction of heat-exchange equipment that is achieved by the following strategies in sequence:introducing heat-exchange equipment directly,adjusting the work quantity of the adjacent utility compressors or expanders,and approximating upper/lower pressure limits consequently to obtain considerable cost savings of expanders or compressors and work utility.Finally,a case taken from the literature is studied to illustrate the feasibility and effectiveness of the proposed method.
